JP2000038420A - Propylene copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene copolymer having excellent moldability and high transparency and uniformity and useful also as a compatibilizing agent. SOLUTION: The objective propylene graft copolymer containing terminal vinyl group originating from propylene and C-C double board originating from diolefin satisfies the following requirements. (a) The weight-average molecular weight is 1,500-500,000; (b) the content of unit originating from diolefins is 0-20 mol.%; (c) the content of unit originating from 2-20C α-olefins (excluding propylene), cycloolefins and styrene monomers is 0-50 mol.%; and (d) the product [η].[C] is 0.01-5 wherein [η] is intrinsic viscosity (decalin L/g) and [C] is the sum of the terminal vinyl group originating from propylene and the C-C double bond originating from diolefins. The propylene graft copolymer includes a copolymer produced by copolymerizing propylene, etc., to the above propylene polymer, having a boiling xylene insoluble content of <=1%, essentially free from gel and containing 0.01-80 wt.% of the above propylene copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer and a method for producing the same, and more particularly, it can control the activation energy of the flow of a melt arbitrarily, can perform high-speed molding, and has a low processing cost. The present invention also relates to a propylene-based copolymer and a propylene-based graft copolymer having transparency and uniformity, and a method for efficiently producing these copolymers.

[0002]

2. Description of the Related Art Conventionally, polypropylene has (1) high mechanical strength such as rigidity and excellent physical property balance;
(2) It is chemically stable, has excellent weather resistance and is not easily attacked by chemicals, etc. (3) It has a high melting point and excellent heat resistance.
(4) It is widely used in many fields because it has features such as light weight and inexpensiveness, is excellent in melt moldability, and can be applied to melt molding methods such as injection molding and cast molding.

[0003] Also, imparting new properties (especially melt tension)
As a result, resin design has been made to fully utilize the inherent properties of polypropylene and to expand to a wider range of applications. For example, JP-A-5-185490, 5-1.
Nos. 94659 and 5-194778, 5-
Nos. 194793 and 5-200849, Method 5
JP-A-202137, JP-A-5-202143, JP-A-5-202219, JP-A-5-202237,
JP-A-5-202238, JP-A-5-202248, JP-A-5-209062, JP-A-5-212771, JP-A-5-212774, JP-A-5-214178
JP-A-5-220829, JP-A-5-220829
No. 1, No. 5-222122, No. 5-22222
Nos. 51, 5-22895, 5-237
In JP-A-930 and JP-A-5-239232, a propylene-based polymer and a resin composition containing the polymer are imparted with improved melt tension by combining a prepolymerization catalyst and a prepolymerization method. A technique for performing this is disclosed.

[0004] However, in the techniques disclosed in these publications, the pre-polymerization operation before the main polymerization is performed in at least three steps, and the operation is complicated.
In general, there is a problem that a chain non-conjugated diene which is poor in reactivity and has a risk of cyclization or crosslinking reaction during the reaction is used as it is.

[0005]

SUMMARY OF THE INVENTION Under such circumstances, the present invention can arbitrarily control the activation energy of the flow of a melt, enables high-speed molding, reduces processing costs, and reduces the processing cost. A propylene copolymer having good thermal stability, transparency and uniformity, and a block polypropylene, a propylene copolymer excellent in compatibility between different polyolefins, and a method for efficiently producing this at the same time. It was made for the purpose of providing.

The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, they have a structure comprising a terminal vinyl unit derived from propylene and a carbon-carbon double bond unit derived from diolefin. Controlling the weight-average molecular weight, unit content derived from diolefin, content of units derived from olefins other than propylene to a certain range, and vinyl groups and carbon-carbon double bonds observed in the copolymer The product of the total viscosity and the intrinsic viscosity is a propylene-based copolymer having a specific relationship and a propylene-based graft copolymer obtained by graft-polymerizing an olefin to the copolymer has the above-described preferable properties, and It has been found that these can be efficiently produced by using a specific polymerization catalyst. The present invention has been completed based on such findings.

That is, the present invention provides at least a terminal vinyl group derived from propylene and a carbon-
A polymer containing a carbon double bond, comprising the following (a) to
(D) (a) a weight average molecular weight of 1500 to 500000,
(B) the content of units derived from diolefin is 0 mol%
(C) the content of units derived from α-olefins having 2 to 20 carbon atoms other than propylene, a cyclic olefin and a styrene monomer is 0 to 50 mol% and (d) a decalin solvent Of the intrinsic viscosity [η] (deciliter / g) measured in the above and the sum [C] of the content of the terminal vinyl group derived from propylene and the carbon-carbon double bond derived from the diolefin [C] [C] Satisfies 0.01 to 5, a propylene-based copolymer (I), and the propylene-based copolymer has an α-olefin, a cyclic olefin, or a styrene-based monomer having 2 to 20 carbon atoms. Having a boiling xylene-insoluble portion of 1% or less and containing substantially no gel, and having a propylene-based copolymer content of 0.01 to 80% by weight. Polymer (II) It is intended to provide.

Further, the present invention relates to (A) at least one selected from transition metal compounds belonging to Group 4 of the periodic table having a cyclopentadienyl group, and (B) an aluminum oxy compound (B-1). , (B-2) an ionic compound which can be converted into a cation by reacting with the above transition metal compound, and (B-2)
-3) Copolymerization of propylene and diolefin, or propylene and diolefin, and other than propylene in the presence of a polymerization catalyst containing at least one selected from clay, clay mineral, and ion-exchange layered compound Carbon number 2
To produce the propylene-based copolymer (I) by copolymerizing at least one of α-olefins, cyclic olefins and styrene-based monomers of (A) to (C), and (A) a cycle having a cyclopentadienyl group At least one selected from transition metal compounds of Group 4 of the
-1) an aluminum oxy compound, (B-2) an ionic compound which can be converted to a cation by reacting with the transition metal compound, and (B-3) a clay, a clay mineral or an ion-exchangeable layered compound clay mineral. Propylene and a diolefin are copolymerized in the presence of the first polymerization catalyst containing at least one of the above-mentioned propylene-based copolymers (I) to form the propylene-based copolymer (I). In the presence or in the presence of a solid catalyst component comprising titanium, magnesium and an electron donating compound, an organoaluminum compound and a second polymerization catalyst comprising an electron donating compound as a third component, the copolymer further comprises carbon atoms. 2-20 α-
An object of the present invention is to provide a method for producing the propylene-based graft copolymer (II) by graft-polymerizing an olefin, a cyclic olefin or a styrene-based monomer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene-based copolymer (I) and the propylene-based graft copolymer (II) of the present invention require propylene and diolefins as raw material monomers, and further have 2 carbon atoms other than propylene. ~ 20 α-
An olefin, a cyclic olefin and a styrene monomer are used. The diolefins are selected from compounds formed from at least two same or different residues selected from α-olefin residues, styrene residues and cyclic olefin residues, and cyclic diene compounds. The preferred polyfunctional monomers are preferably used. Examples of such polyfunctional monomers include linear or branched acyclic diene compounds, monocyclic alicyclic diene compounds, polycyclic alicyclic diene compounds, cycloalkenyl-substituted alkenes, and aromatic rings. And a diene compound having an α-olefin residue and a styrene residue in one molecule.

The linear or branched acyclic diene compound includes, for example, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene,
1,9-decadiene, 1,11-dodecadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,5-hexadiene, 3-ethyl-1,7-octadiene and the like, and a monocyclic alicyclic ring Examples of the formula diene compound include 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-cyclododecadiene, 1,2-divinylcyclohexane, 1,3
-Divinylcyclohexane and the like.

Further, as the polycyclic alicyclic diene compound,
For example, dicyclopentadiene, norbornadiene, tetrahydroindene, methyltetrahydroindene, 5-
Methyl-2,5-norbornadiene, and also norbornenes of alkenyl, alkylidene, cycloalkenyl and cycloalkylidene, such as 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene , 5-vinylnorbornene, 5- (3-butenyl) norbornene, 5- (3-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, and formula

[0012]

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And the like. Examples of cycloalkenyl-substituted alkenes include allylcyclohexene, vinylcyclooctene, allylcyclodecene, vinylcyclododecene, and the like.Examples of diene compounds having an aromatic ring include p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, di- (p-vinylphenyl) methane, 1,3-bis (p-vinylphenyl) propane, 1,5-bis (p-
Vinylphenyl) pentane and the like.

As a diene compound having an α-olefin residue and a styrene residue in one molecule, for example, p- (2
-Propenyl) styrene, m- (2-propenyl) styrene, p- (3-butenyl) styrene, m- (3-butenyl) styrene, o- (3-butenyl) styrene, p-
(4-pentenyl) styrene, m- (4-pentenyl)
Styrene, o- (4-pentenyl) styrene, p- (7
-Octenyl) styrene, p- (1-methyl-3-butenyl) styrene, p- (2-methyl-3-butenyl) styrene, m- (2-methyl-3-butenyl) styrene,
o- (2-methyl-3-butenyl) styrene, p- (3
-Methyl-3-butenyl) styrene, p- (2-ethyl-4-pentenyl) styrene, p- (3-butenyl)-
α-methylstyrene, m- (3-butenyl) -α-methylstyrene, o- (3-butenyl) -α-methylstyrene, 4-vinyl-4 ′-(3-butenyl) biphenyl,
4-vinyl-3 '-(3-butenyl) biphenyl, 4-
Vinyl-4 '-(4-pentenyl) biphenyl, 4-vinyl-2'-(4-pentenyl) biphenyl, 4-vinyl-4 '-(2-methyl-3-butenyl) biphenyl and the like. These diolefins may be used alone or in combination of two or more.

Examples of the α-olefin having 2 to 20 carbon atoms excluding propylene include ethylene, 1-butene, 1-
Pentene, 4-methyl-1-pentene, 1-hexene,
Examples include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. As the cyclic olefin,
Those having 3 to 20 carbon atoms are preferred. Specifically, cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 5,6-dimethylnorbornene, 5,5,6
-Trimethylnorbornene, 5-ethylnorbornene,
5-propylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, and the like. Examples of the styrene-based monomer include styrene and derivatives thereof (having substituents containing carbon, halogen, silicon, and the like), specifically, styrene, p-methylstyrene, o-
Alkylstyrene such as methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, pt-butylstyrene, p-chloro Styrene, m-chlorostyrene, o-chlorostyrene, p-
Bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene,
Examples thereof include halogenated styrenes such as o-fluorostyrene and o-methyl-p-fluorostyrene, and vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl. In the present invention, one of these monomers may be used alone, or two or more thereof may be used in combination.

In order to produce the propylene-based copolymer (I) of the present invention, the polymerization catalyst is selected from (A) transition metal compounds belonging to Group 4 of the periodic table having a cyclopentadienyl group. (B) (B-1) an aluminum oxy compound, (B-2) an ionic compound which can be converted to a cation by reacting with the transition metal compound, and (B)
-3) It is preferable to use a polymerization catalyst containing at least one selected from clay, clay minerals and ion-exchange layered compounds. For the production of the propylene-based graft copolymer (II), the same polymerization catalyst as described above or a solid catalyst component containing titanium, magnesium and an electron donating compound as essential components, an organoaluminum compound and a third catalyst are used. It is preferable to use a polymerization catalyst comprising an electron donating compound as a component.

Examples of the transition metal compounds belonging to Group 4 of the periodic table having a cyclopentadienyl group of the component (A) include the following components (A-1), (A-2), and (A-
One type selected from component 3) and component (A-4) can be mentioned. Component (A-1): The component (A-1) is represented by the general formula (I)

[0018]

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[Wherein, R¹~ R⁶Are each independently water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or
Represents a halogen-containing hydrocarbon group having 1 to 20 carbon atoms;
^ThreeAnd R ^Four, R^FourAnd R^FiveAnd R^FiveAnd R⁶At least of
May be bonded to each other to form a ring;¹Passing
And X^TwoAre each independently a hydrogen atom, halogen atom or charcoal
Y represents a hydrocarbon group having a prime number of 1 to 20,¹Is two ligands
A divalent cross-linking group that binds
A hydride group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,
Silicon-containing group, germanium-containing group, tin-containing group, -O
-, -CO-, -S-, -SO_Two-, -Se-, -N
R'-, -PR'-, -P (O) R'-, -BR'- or
Represents -AlR'-, and R 'represents a hydrogen atom or a halogen atom.
, A hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms.
And a hydrogen-containing hydrocarbon group. M¹Is titanium, zirconi
Or hafnium. The transition metal compound represented by
Things.

In the general formula (I), R ³ and R ⁴ , R ⁴
A transition metal compound in which at least one pair formed a ring of R ⁵ and R ⁵ and R ⁶ is a compound known as BASF type complex. In the general formula (I), R ¹
Examples of the halogen atom in R ⁶ include chlorine, bromine, fluorine, and iodine atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group, and an n-decyl group. Alkyl group, phenyl group, 1-naphthyl group, 2
-An aryl group such as a naphthyl group, an aralkyl group such as a benzyl group, and the like. As the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom of the hydrocarbon group is a suitable halogen atom And a group substituted with R ^{1 to} R ⁶ may be the same or different from each other, and at least one of adjacent groups, ie, R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ^6. The pairs need to be linked to each other to form a ring. Examples of such an indenyl group forming a ring include a 4,5-benzoindenyl group, an α-acenaphthoindenyl group, and an alkyl-substituted product having 1 to 10 carbon atoms.

The halogen atom in X ¹ and X ² includes chlorine, bromine, fluorine and iodine atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group and n-hexyl group, and aryl groups such as phenyl group. And an aralkyl group such as a benzyl group. X ¹ and X ² may be the same or different. On the other hand, Y ¹ is a divalent group bonding two ligands, and among them, examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a methylene group; a dimethylmethylene group; An ethylene group; a dimethyl-1,2-ethylene group; a 1,4-tetramethylene group; an alkylene group such as a 1,2-cyclopropylene group,
Examples include an arylalkylene group such as a diphenylmethylene group, and examples of the divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms include a chloroethylene group and a chloromethylene group. Examples of the divalent silicon-containing group include a methylsilylene group, a dimethylsilylene group,
Examples include a diethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group. Further, examples of the germanium-containing group and the tin-containing group include groups obtained by converting silicon into germanium and tin in the above-mentioned silicon-containing group. The two ligands bonded by Y ¹ are usually the same, but may be different depending on the case.

As the transition metal compound represented by the general formula (I) of the component (A-1), for example, JP-A-6-18
Compounds described in JP-A-4179 and JP-A-6-345809 can be exemplified. As a specific example, rac-dimethylsilanediyl-bis-1-
(2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-phenylmethylsilanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-ethanediyl-bis -1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-butanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-dimethylsilanediyl -Bis-1- (4,5-benzoindenyl)-
Zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2-methyl-α-methyl-α-acenaphthoindenyl) -zirconium dichloride, rac-
Benzoindenyl- or acenaphthoindenyl-type compounds such as phenylmethylsilanediyl-bis-1- (2-methyl-α-acenaphthoindenyl) -zirconium dichloride, and zirconium in these compounds is replaced by titanium or hafnium And the like.

The component (A-1) is a compound represented by the formula (I), wherein R ³ and R ⁴ , R ⁴ and R ⁵ and R ⁵ and R
^The transition metal compound having an indenyl skeleton in which none of the groups forms a ring, or the corresponding 4,5,6,
It is a transition metal compound having a 7-tetrahydroindenyl skeleton. This transition metal compound is a compound known as a Hoechst complex. Examples of the transition metal compound of the component (A-1) include, for example, JP-A-4-26830.
No. 8, No. 5-306304, No. 6-1005
No. 79, 6-157661, 7-149
No. 815, No. 7-188318, No. 7-25
Compounds described in 8321 and the like can be mentioned. As a specific example, dimethylsilanediyl-
Bis-1- (2-methyl-4-phenylindenyl)-
Zirconium dichloride, dimethylsilanediyl-bis-1- [2-methyl-4- (1-naphthyl) indenyl] -zirconium dichloride, dimethylsilanediyl-bis-1- (2-ethyl-4-phenylindenyl)
-Zirconium dichloride, dimethylsilanediyl-bis-1- [2-ethyl-4- (1-naphthyl) indenyl] zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-methyl-4-phenylindenyl)- Zirconium dichloride, phenylmethylsilanediyl-bis-1- [2-methyl-4- (1-naphthyl) indenyl] -zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-ethyl-4-phenylindenyl) -Zirconium dichloride, phenylmethylsilanediyl-bis-1- [2-ethyl-4-
Aryl-substituted products such as (1-naphthyl) indenyl] -zirconium dichloride, rac-dimethylsilylene-
Bis-1- (2-methyl-4-ethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methyl-4-isopropylindenyl)
-Zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methyl-4-tert-butylindenyl) -zirconium dichloride, rac-phenylmethylsilylene-bis-1- (2-methyl-4-isopropylindenyl) ) -Zirconium dichloride, rac-dimethylsilylene-bis-1- (2-ethyl-4-methylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2,4-dimethylindenyl) -zirconium dichloride 2,4-position substituents such as, rac-dimethylsilylene-bis-1- (2-methyl-4-ethylindenyl) -zirconium dimethyl,
rac-dimethylsilylene-bis-1- (4,7-dimethylindenyl) -zirconium dichloride, rac-
1,2-ethanediyl-bis-1- (2-methyl-4,
7-dimethylindenyl) -zirconium dichloride,
rac-dimethylsilylene-bis-1- (3,4,7-
Trimethylindenyl) -zirconium dichloride, r
ac-1,2-ethanediyl-bis-1- (4,7-dimethylindenyl) -zirconium dichloride, rac
4,7, such as -1,2-butanediyl-bis-1- (4,7-dimethylindenyl) -zirconium dichloride
-Position, 2,4,7-position or 3,4,7-position substituent, dimethylsilanediyl-bis-1- (2-methyl-4,6-
Diisopropylindenyl) -zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2-methyl-4 , 6-Diisopropylindenyl) -zirconium dichloride, rac-1,2-ethanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac
-Diphenylsilanediyl-bis-1- (2-methyl-
4,6-diisopropylindenyl) -zirconium dichloride, rac-phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- 2,4,6-substituted product such as (2,4,6-trimethylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1-
2,5,6-substituted product such as (2,5,6-trimethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis- (2-methyl-4,5,6,7-
Tetrahydro-1-indenyl) -zirconium dichloride, rac-ethylene-bis- (2-methyl-4,
5,6,7-tetrahydro-1-indenyl) -zirconium dichloride, rac-dimethylsilylene-bis-
(2-methyl-4,5,6,7-tetrahydro-1-indenyl) -zirconium dimethyl, rac-ethylene-bis (2-methyl-4,5,6,7-tetrahydro-
1-indenyl) -zirconium dimethyl, rac-ethylene-bis- (4,7-dimethyl-4,5,6,7-
Examples thereof include 4,5,6,7-tetrahydroindenyl compounds such as tetrahydro-1-indenyl) -zirconium dichloride, and compounds obtained by substituting zirconium in these compounds with titanium or hafnium. Component (A-2): Component (A-2) is represented by the general formula (II)

[0024]

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[Wherein, R⁷~ R¹³, R^Fifteen, R¹⁶, X^ThreePassing
And X^FourAre independently a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogen having 1 to 20 carbon atoms
Containing hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing
A nitrogen-containing group or a phosphorus-containing group;⁷And R⁸flag
It may combine with an insulator to form a ring. R¹⁴, R¹⁷Is
Each independently a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
Groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing
Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or
And a thiol-containing group. Y^TwoIs a divalent linking two ligands
A crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
1 to 20 halogen-containing hydrocarbon groups, silicon-containing groups, gels
Manium-containing group, tin-containing group, -O-, -CO-, -S
-, -SO _Two-, -Se-, -NR'-, -PR'-,
Represents -P (O) R'-, -BR'- or -AlR'-.
And R 'is a hydrogen atom, a halogen atom, a C1-20
Hydrocarbon group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms
Is shown. M^TwoIs titanium, zirconium or hafnium
Show. ] It is a transition metal compound represented by these.

This transition metal compound is a single-bridge type complex. In the general formula (II), R ^{7 to} R ¹³ , R ¹⁵ , R
Examples of the halogen atom among ¹⁶ , X ³ and X ⁴ include a chlorine, bromine, fluorine and iodine atom. Carbon number 1
Examples of the hydrocarbon group of No. 20 to No. 20 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, tert-butyl group, n-hexyl group,
Examples thereof include an alkyl group such as n-decyl group, an aryl group such as phenyl group, 1-naphthyl group and 2-naphthyl group, and an aralkyl group such as benzyl group.
Examples of the halogen-containing hydrocarbon group of 0 include groups in which one or more hydrogen atoms of the above-mentioned hydrocarbon groups such as trifluoromethyl are substituted with an appropriate halogen atom. Examples of the silicon-containing group include a trimethylsilyl group and a dimethyl (t-butyl) silyl group, and examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a methylthio group and an ethylthio group. And
Examples of the nitrogen-containing group include a dimethylamino group, and examples of the phosphorus-containing group include a methylphosphine group and a phenylphosphine group. Further, R ⁷ and R ⁸ may be bonded to each other to form a ring such as fluorene.
Specific examples of R ¹⁴ and R ¹⁷ include groups excluding the hydrogen atom from those described above for R ^{7 to} R ^{13 and the} like.
R ⁷ and R ⁸ are preferably a hydrogen atom and an alkyl group having 6 or less carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a cyclohexyl group, and further preferably a hydrogen atom. Further, as R ⁹ , R ¹² , R ¹⁴ and R ¹⁷ , an alkyl group having 6 or less carbon atoms is preferable,
A methyl group, an ethyl group, an isopropyl group and a cyclohexyl group are more preferred, and an isopropyl group is even more preferred.
R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁶ are preferably hydrogen atoms. X ³ and X ⁴ represent a halogen atom, hydrogen,
An alkyl group having 1 to 3 carbon atoms is preferred.

Specific examples of Y ² include methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, tetramethyldisilylene, dimethylgermylene, methylborylidene (CH _3- B =), methylaluminidene (CH
_3- Al =), phenylphosphylidene (Ph-P
=), Phenylphosphoridene (PhPO =), 1,2-
Phenylene, vinylene (-CH = CH-), vinylidene (CH ₂ = C =), methylimide, oxygen (-O-), include sulfur (-S-), among these, methylene,
Ethylene, ethylidene and isopropylidene are preferred in terms of ease of synthesis and yield. M ² represents titanium, zirconium or hafnium, with hafnium being particularly preferred.

Specific examples of the transition metal compound represented by the general formula (II) include 1,2-ethanediyl (1-
(4,7-diisopropylindenyl)) (2- (4,
7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2-
(4,7-diisopropylindenyl) hafnium dichloride, isopropylidene (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2-
(4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl)
(2- (4,7-dimethylindenyl)) hafnium dichloride, isopropylidene (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, and the like, and the like. Examples include, but are not limited to, compounds obtained by substituting hafnium in a compound with zirconium or titanium.The transition metal compound represented by the general formula (II) may be, for example, Application for Japanese Patent Application No. 09
It can be produced by the method described in -296612. Component (A-3): Component (A-3) is represented by the general formula (III)

[0029]

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[Wherein R ¹⁸ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms
Represents an alkylaryl group having from 20 to 20 or an arylalkyl group having from 7 to 20 carbon atoms, and two adjacent R ¹⁸ may form a ring composed of 5 to 8 carbon atoms, and R ¹⁸ is a silicon atom or germanium It may contain atoms. Y ³ is> S
iR ¹⁹ ₂ or> GeR ¹⁹ ₂ (R ¹⁹ is the same or different,
An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 6 carbon atoms
20 aryl group, a cyclic group consisting of optionally alkyl group, or an arylalkyl group having 7 to 20 carbon atoms of 7 to 20 carbon atoms which may contain heteroatoms, up to two of R ¹⁹ is 8 atoms May be formed. However, at least four carbon atoms are included in two R ¹⁹ . ) And M
³ represents titanium, zirconium or hafnium. X ⁵
And X ⁶ are the same or different and are each a halogen atom, -OH,
^{-SH, -R 20, -OR 20,} -SR 20, -NR 20 2 or -PR ²⁰ ₂ (R ²⁰ is. Showing the same as R ¹⁸⁾ shows a. ] It is a transition metal compound represented by these.

In the general formula (III), preferred R ¹⁸
As a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, more preferably a 3 to 6 carbon atoms,
0, more preferably an alkenyl group having 2 to 3 carbon atoms, an aryl group having 8 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. Preferred Y ³ is,> SiR ¹⁹ ₂ or> GeR
In ¹⁹ _2, the number R ¹⁹ is a carbon 1 to 10, more preferably those which are alkyl groups of 4-8 carbon atoms, particularly bis (n- butyl) silanediyl group. M ³ represents titanium, zirconium or hafnium, with zirconium being particularly preferred. X ⁵ and X ⁶ are a halogen atom,
Preferably, R ²⁰ is an alkyl group, particularly preferably a chlorine atom or a methyl group.

Specific examples of the transition metal compound represented by the general formula (III) include dimethylsilanediylbis (fluorenyl) titanium dichloride, dimethylsilanediylbis (fluorenyl) zirconium dichloride, and dimethylsilanediylbis (fluorenyl) hafnium. Dichloride, diethylsilanediylbis (fluorenyl) titanium dichloride, diethylsilanediylbis (fluorenyl) zirconium dichloride, diethylsilanediylbis (fluorenyl) hafnium dichloride, diethylsilanediylbis (fluorenyl) titanium dimethyl, diethylsilanediylbis (fluorenyl) zirconium Dimethyl, diethylsilanediylbis (fluorenyl) hafnium dimethyl, di (n-propyl) silanediylbis (fluorenyl) thiamine Njikurorido, di (n- propyl) silanediylbis (fluorenyl) zirconium dichloride, di (n- propyl) silanediylbis (fluorenyl) hafnium dichloride, di (n- propyl)
Silanediylbis (fluorenyl) titanium dimethyl, di (n-propyl) silanediylbis (fluorenyl) zirconium dimethyl, di (n-propyl) silanediylbis (fluorenyl) hafnium dimethyl, di (n-butyl) silanediylbis (fluorenyl) titanium dichloride, di (n- Butyl) silanediylbis (fluorenyl) zirconium dichloride, di (n-butyl) silanediylbis (fluorenyl) hafnium dichloride, di (n-butyl) silanediylbis (fluorenyl) titanium dimethyl, di (n-butyl) silanediylbis (fluorenyl) zirconium dimethyl, di ( n-butyl) silanediylbis (fluorenyl) hafnium dimethyl,
Methyl (n-butyl) silanediylbis (fluorenyl) titanium dichloride, methyl (n-butyl) silanediylbis (fluorenyl) zirconium dichloride, methyl (n-butyl) silanediylbis (fluorenyl)
Hafnium dichloride, methyl (n-butyl) silanediylbis (fluorenyl) titanium dimethyl, methyl (n
-Butyl) silanediylbis (fluorenyl) zirconium dimethyl, methyl (n-butyl) silanediylbis (fluorenyl) hafnium dimethyl, methyl (n-hexyl) silanediylbis (fluorenyl) titanium dichloride, methyl (n-hexyl) silanediylbis (fluorenyl) zirconium dichloride, methyl (N-hexyl) silanediylbis (fluorenyl) hafnium dichloride, methyl (n-octyl) silanediylbis (fluorenyl) titanium dichloride, methyl (n-octyl) silanediylbis (fluorenyl) zirconium dichloride, methyl (n-octyl) silanediylbis (fluorenyl) hafnium dichloride , Diethylgermandiylbis (fluorenyl) titanium dichloride, diethylgermandi Bis (fluorenyl) zirconium dichloride, diethyl germane diyl bis (fluorenyl) hafnium dichloride, diethyl germane diyl bis (fluorenyl) titanium dimethyl, diethyl germane diyl bis (fluorenyl) zirconium dimethyl,
Diethylgermandiylbis (fluorenyl) hafnium dimethyl, diethylsilanediylbis (1-methylfluorenyl) titanium dichloride, diethylsilanediylbis (1-methylfluorenyl) zirconium dichloride, diethylsilanediylbis (1-methylfluoride Nyl) hafnium dichloride, diethylsilanediylbis (1-methylfluorenyl) titanium dimethyl, diethylsilanediylbis (1-methylfluorenyl) zirconium dimethyl, diethylsilanediylbis (1-methylfluorenyl) hafnium dimethyl, etc. Is mentioned.
Component (A-4): Component (A-4) is represented by the general formula (IV)

[0033]

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[Wherein, M^ThreeIs titanium, zirconium or
Indicates hafnium, E¹And E^TwoAre each substituted cyclo
Pentadienyl group, indenyl group, substituted indenyl group,
Heterocyclopentadienyl group, substituted heterocyclopen
Tadienyl group, amide group, phosphide group, hydrocarbon group and
A ligand selected from the group consisting of¹Passing
And A^TwoForm a cross-linked structure through
They may be the same or different, X⁷Is σ connectivity
A ligand of X⁷If there are multiple Xs ⁷Is the same
Same or different, other X⁷, E¹, E^TwoOr
Y^FourAnd may be crosslinked. Y^FourRepresents a Lewis base,
Y^FourIf there is more than one,^FourAre the same but different
May be other Y^Four, E¹, E^TwoOr X⁷Cross-linked with
A¹And A^TwoIs a divalent linking two ligands
A hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group of 1 to 20; a silicon-containing group;
Rumanium-containing group, tin-containing group, -O-, -CO-,-
S-, -SO_Two-, -Se-, -NR'-, -PR '
-, -P (O) R'-, -BR'- or -AlR'-
R ′ is a hydrogen atom, a halogen atom, and has 1 to 20 carbon atoms.
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Denote groups, which may be the same or different
No. q is an integer of 1 to 5 [(M^ThreeValence) -2]
And r represents an integer of 0 to 3. Transition metallization represented by
Compound (hereinafter, may be referred to as a double-bridged complex).
is there.

In the general formula (IV), M ³ is titanium,
Zirconium or hafnium, but zirconium,
Hafnium is preferred. As described above, E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, and an amide group (−
N <), phosphide group (-P <), hydrocarbon group [> CR
-,> C <] and silicon-containing groups [>SiR-,> Si <]
Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a heteroatom-containing group, and represents a ligand selected from A ¹ and A ² to form a crosslinked structure. I have. E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred.

Also, X⁷Σ-binding ligand tool represented by
Examples of the body include a halogen atom, a hydrocarbon having 1 to 20 carbon atoms.
Element group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, C1-20 amide group, carbon
A silicon-containing group having 1 to 20 carbon atoms, a phosphide having 1 to 20 carbon atoms
Group, a sulfide group having 1 to 20 carbon atoms, and a sulfide group having 1 to 20 carbon atoms
Acyl groups and the like. This X⁷If there are multiple
Multiple X⁷May be the same or different, and other X⁷,
E¹, E^TwoOr Y^FourAnd may be crosslinked. On the other hand, Y^Four
Specific examples of Lewis bases represented by
-Tels, phosphines, thioethers, etc.
be able to. This Y^FourIf there is more than one,^FourIs
May be the same or different, other Y^FourAnd E¹, E^Twoor
Is X ⁷And may be crosslinked. Next, A¹And A^TwoIndicated by
At least one of the cross-linking groups to be formed has at least one carbon atom.
It is preferably a cross-linking group comprising a hydrocarbon group. this
As such a crosslinking group, for example, a general formula

[0037]

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(R ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ^{21 s} may be the same or different, and may combine with each other to form a ring structure. And e represents an integer of 1 to 4.), and specific examples thereof include a methylene group, an ethylene group,
Ethylidene group, propylidene group, isopropylidene group,
A cyclohexylidene group, a 1,2-cyclohexylene group,
And a vinylidene group (CH ₂ ＣC な ど). Among them, a methylene group, an ethylene group and an isopropylidene group are preferred. A ¹ and A ² may be the same or different. In the transition metal compound represented by the general formula (IV), when E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the bond of the cross-linking group of A ¹ and A ² is
(1,1 ′) (2,2 ′) may be a double crosslinked type,
The (1,2 ′) (2,1 ′) double cross-linking type may be used.
Among the transition metal compounds represented by the general formula (IV), the general formula (IV-a)

[0039]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferable. In the above general formula (IV-a), M ³ , A ¹ , A ² ,
q and r are the same as above. X ⁷ represents a σ-bonding ligand, and when X ⁷ is more, the plurality of X ⁷ may be the same or different, may be crosslinked with other X ⁷ or Y ^4. Specific examples of X ⁷ include the same as those exemplified in the description of X ^{7 in} general formula (IV).
Y ⁴ represents a Lewis base, if Y ⁴ is more, the plurality of Y ⁴ may be the same or different, the other Y ⁴ or X ⁷
And may be crosslinked. Specific examples of Y ⁴ include the same as those exemplified in the description of Y ^{4 in} the general formula (IV). R ²² to R ²⁷ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-2
0 represents a halogen-containing hydrocarbon group, a silicon-containing group or a heteroatom-containing group, and at least one of them must not be a hydrogen atom. Further, R ^{22 to} R ²⁷ may be the same or different, and adjacent groups may be bonded to each other to form a ring.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand has a ligand of (1,1 ′) (2,2 ′) double-bridged type or (1,2 ′). ')
Any of the (2,1 ′) double cross-linking type may be used. Specific examples of the transition metal compound represented by the general formula (IV) include (1,1′-ethylene) (2,2′-ethylene)-
Bis (indenyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,2 ′ -Methylene) (2,
1′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2 ′
-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-isopropylidene) (2,
1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1'-ethylene) (2,2 '
-Ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
(Ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′- Ethylene) (2,1'-
Ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2 ′
-Ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2
1'-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1'-ethylene)
(2,2′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium Dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4 -Phenylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'- Ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-ethylene) -bis (5
6-benzoindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-isopropylidene) -bis ( Indenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride,
(1,1′-isopropylidene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride,
(1,2′-methylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-
Methylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene)
(2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-
(Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2 ′) −
Methylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene)
(3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) (3-methylcyclopentadienyl) (cyclopentadienyl )
Zirconium dichloride, (1,1'-propylidene)
(2,2′-propylidene) (3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-methylene) -bis (3-methylcyclopenta Dienyl) zirconium dichloride, (1,1′-methylene) (2,2 ′
-Ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1 ,
1′-ethylene) (2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene) -bis (3-methyl Cyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2 ′
-Isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1'-isopropylidene) (2,2'-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-methylene) -bis (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (1,1'-ethylene)
(2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,1′-methylene) (2,2′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2′-isopropylidene)- Bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, 1,2′-ethylene) (2,1′-
Methylene) -bis (3-methylcyclopentadienyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,
2'-methylene) (2,1'-methylene) -bis (3-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene)
(2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-methylene) -bis (3
4-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2′- Methylene) (2,1′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,2′-methylene) (2,1′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (3,4-
Dimethylcyclopentadienyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium can be mentioned. Of course, it is not limited to these.

In the polymerization catalyst of the present invention,
As the transition metal compound of the component (A), preferably, the component (A-1) (BASF type complex or Hoechst type complex), the component (A-2) (single crosslinked type complex), the component (A-3) and At least one selected from the components (A-4) (double crosslinked complexes) is used. When using one kind,
When producing a propylene-based copolymer (I) having an isotactic structure, (A-1) a BASF-type complex, a Hoechst-type complex, (A-2) a single-bridge type complex, and (A-4) a double-bridge type. The complex is preferably a hafnium compound of the above complex, and when producing the propylene copolymer (I) having an atactic structure, the component (A-3) is preferred. When two or more kinds are used, a combination of a zirconium compound-hafnium compound, a zirconium compound-zirconium compound, a hafnium compound-hafnium compound is particularly preferable.

Preferred examples of such a combination include:
Mono-bridged zirconium complex-mono-bridged hafnium complex,
BASF zirconium complex-BASF hafnium complex, Hoechst zirconium complex-Hoechst hafnium complex, single bridge zirconium complex-BASF hafnium complex, single bridge zirconium complex-Hoechst hafnium complex, BASF zirconium complex-single bridge Hafnium complex, Hoechst-type zirconium complex-single-bridged hafnium complex, BASF-type zirconium complex-double-bridged hafnium complex, Hoechst-type zirconium complex-double-bridged hafnium complex, single-bridged zirconium complex-
Double-bridged hafnium complex, double-bridged zirconium complex-double-bridged hafnium complex, double-bridged zirconium complex-BASF-type hafnium catalyst, double-bridged zirconium complex-Hoechst-type hafnium catalyst, double-bridged zirconium Complex-single-bridged hafnium complex, single-bridged zirconium complex-single-bridged zirconium complex, BASF
-Type zirconium complex-BASF-type zirconium complex, Hoechst-type zirconium complex-Hoechst-type zirconium complex, BASF-type zirconium complex-single-bridged zirconium complex, Hoechst-type zirconium complex-single-bridged zirconium complex, BASF-type zirconium complex-double-bridged type Zirconium complex, Hoechst-type zirconium complex-double-bridged zirconium complex, double-bridged zirconium complex-single-bridged zirconium complex, double-bridged zirconium complex-double-bridged zirconium complex, single-bridged hafnium complex-single-bridged -Type hafnium complex, BASF-type hafnium complex-BASF-type hafnium complex, Hoechst-type hafnium complex-Hoechst-type hafnium complex, BASF-type hafnium complex-single-bridge type hafnium complex, Hoechst-type hafnium complex-single -Type hafnium complex, BASF-type hafnium complex-double-bridged hafnium complex, Hoechst-type hafnium complex-double-bridged hafnium complex, double-bridged hafnium complex-single-bridged hafnium complex, double-bridged hafnium complex-double Crosslinked hafnium complexes and the like can be mentioned.

In the polymerization catalyst of the present invention,
As the component (B), (B-1) an aluminum oxy compound, (B-2) an ionic compound which can be converted to a cation by reacting with the transition metal compound, and (B-3) a clay, a clay mineral or an ion-exchange compound At least one selected from layered compounds is used. The aluminum oxy compound of the component (B-1) is represented by the general formula (V):

[0045]

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(Wherein R ²⁸ represents an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. Each R ²⁸ may be the same or different. Aluminoxane represented by the general formula (VI):

[0047]

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(In the formula, R ²⁸ and w are the same as those in the general formula (V).) Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be performed according to a known method. For example, a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organoaluminum compound initially during polymerization and then adding water, and a method of crystal water contained in a metal salt or the like A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. The aluminoxane may be insoluble in toluene.

These aluminum oxy compounds may be used alone or in combination of two or more.
On the other hand, as the component (B-2), any compound can be used as long as it is an ionic compound that can be converted into a cation by reacting with the transition metal compound, and particularly, a polymerization active site can be formed efficiently. From the following general formula (VII),
(VIII) ([L ¹ -R ²⁹ ] ^{h +} ) _a ([Z] ^- ) _b ... (VII) ([L ² ] ^{h +} ) _a ([Z] ^- ) _b ... (VIII) (However , L ² is ^{M 5, R 30 R 31 M} 6, R 32 3 C or R ³³
It is an M ^6. [(VII), (VIII) wherein L ¹ is a Lewis base and [Z] ⁻
Is a non-coordinating anion [Z ^{1] -} or [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element, i.e. ^{[M 4 G 1 G 2 ··· G} f (Where M ⁴ is an element of Groups 5 to 15 of the Periodic Table, preferably 13 to 15 of the Periodic Table)
Shows Group 15 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
A dialkylamino group having 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, and having 7 to 40 carbon atoms. Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
⁴ ) +1]. ), [Z ² ] ^-
It represents a conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having _a logarithm (pKa) of the reciprocal of the acid dissociation constant of -10 or less, or a conjugate base generally defined as a super strong acid. Further, a Lewis base may be coordinated. R ²⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and R ³⁰ and R ³¹ each represent a cyclopentadienyl group, A cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ³² represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ³¹ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. h is an ionic valence of [L ¹ -R ²⁷ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (h × a). M ⁵ are those containing a periodic table Group 1～3,11～13,17 element, M ⁶ represents a periodic table 7-12 group element. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ²⁹ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ³⁰ and R ³¹ include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ³² include a phenyl group, a p-tolyl group and a p-methoxyphenyl group, and specific examples of R ³¹ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ⁵ include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ⁶ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ⁴ G ¹ G
² ... G ^f ], B and A are specific examples of M ^4.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, a p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetate anion (CF ₃ C
O ₂ ) ^- , hexafluoroantimony anion (SbF ₆ )
^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ / S
bF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride (CF ₃ SO ₃ / Sb
F ₅₎ ^-, and the like.

Specific examples of the compound of the component (B-2) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and tetraphenylammonium. Methyl (tri-n-butyl) ammonium borate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, tetraphenyl Methylpyridinium borate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) Triethylammonium borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Tetraethylammonium, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate,
Methylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Benzylpyridinium, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), tetrakis ( Triphenylphosphonium pentafluorophenyl) borate, dimethyl tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate Nilinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocete) ), Decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Sodium, manganese tetraphenylporphyrin, tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, Kisafuruoro arsenic, silver perchlorate, silver trifluoroacetate, and the like of silver trifluoromethanesulfonate.

As the component (B-2), an ionic compound which can be converted into a cation by reacting with the transition metal compound of the component (A) may be used alone or in combination of two or more. Is also good. As the component (B-3), clay, clay mineral or ion-exchange layered compound is used. Clay is an aggregate of fine hydrated silicate minerals, which is a substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Also,
The clay mineral is a hydrated silicate that is a main component of clay. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and means a compound whose contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These are not limited to natural products,
It may be artificially synthesized. Examples of the ion-exchangeable layered compound include an ion-forming compound having a layered crystal structure such as a hexagonal close-packing type, an antimony type, a cadmium chloride type, and a cadmium iodide type.

Specific examples of the component (B-13) include kaolin, bentonite, Kibushi clay, gairome clay, allophane, hysingelite, pyrophyllite, talc, plum group, montmorillonite group, vermiculite, ryokudeite group, and palygorskite. , Nacrite, dickite, halloysite and the like. As the component (B-3), a pore volume having a radius of 20 ° or more measured by a mercury intrusion method is preferably 0.1 ml / g or more, particularly preferably 0.3 to 5 ml / g or more. It is also preferable to carry out a chemical treatment from the viewpoint of removing impurities from the clay or changing the structure and function. Here, the chemical treatment refers to both surface treatment for removing impurities attached to the surface and treatment for affecting the crystal structure of clay. In particular,
Acid treatment, alkali treatment, salt treatment, organic matter embedding, and the like are included. The acid treatment removes surface impurities and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. The alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and organic matter treatment, an ionic complex, a molecular complex, an organic complex, etc. are formed, and the surface area and interlayer distance are reduced. Can be changed. By utilizing the ion exchange property and replacing the exchangeable ions in the layers with another bulky ion, it is possible to obtain an interlayer material in which the layers are expanded. Still further, it is also possible to secure a polymerization reaction field where the main catalyst is present between the layers.

The above-mentioned component (B-3) may be used as it is, or may be used by adding and adsorbing water.
Alternatively, ripened and dehydrated ones may be used. (B
-3) As the component, preferred are clay or clay mineral, and most preferred is montmorillonite.
The component (B-13) is preferably treated with a silane compound and / or an organoaluminum compound. This treatment may improve the activity. Examples of the silane compound include trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, te
Trialkylsilyl chlorides such as rt-butyldiphenylsilyl chloride and phenethyldimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, bisdiphenethylsilyl dichloride, methylphenethylsilyl dichloride, diphenylsilyl dichloride, dimesitylsilyl Dialkylsilyl dichlorides such as dichloride and ditolylsilyl dichloride, methylsilyl trichloride, ethylsilyl trichloride, isopropylsilyl trichloride, phenylsilyl trichloride, mesitylsilyl trichloride, tolysilyl trichloride, phenethylsilyl trichloride and the like Alkyl silyl trichlorides, halides in which the above-mentioned chloride portion is replaced by another halogen element, bis Trimethylsilyl) amine, bis (triethylsilyl) amine, bis (triisopropylsilyl) amine, bis (dimethylethylsilyl) amine, bis (diethylmethylsilyl) amine, bis (dimethylphenylsilyl) amine, bis (dimethyltolylsilyl) amine , Bis (dimethylmesitylsilyl) amine, silylamines such as N, N-dimethylaminotrimethylsilane, (diethylamino) trimethylsilane, N- (trimethylsilyl) imidazole, and polysilanols commonly used as peralkylpolysiloxypolyol , Tris (trimethylsiloxy) silanol and other silanols, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- (trimethylsilyl) acetamide Amide, bis (trimethylsilyl) urea, silylamides inclined such trimethylsilyl diphenylurea, linear siloxanes such as 1,3-dichlorotetramethyldisiloxane, cyclic siloxanes such as pentamethyl cyclopentane siloxane,
Tetraalkylsilanes such as dimethyldiphenylsilane, diethyldiphenylsilane, diisopropyldiphenylsilane, etc., trimethylsilane, triethylsilane, triisopropylsilane, tri-t-butylsilane, triphenylsilane, tolylsilane, trimesitylsilane, methyldiphenylsilane, Examples thereof include trialkylsilanes such as dinaphthylmethylsilane and bis (diphenyl) methylsilane, and inorganic silicon compounds such as silicon tetrachloride and silicon tetrabromide. Of these, preferred are silylamines, and more preferred are trialkylsilane chlorides. One of these silane compounds may be used, but in some cases, two or more of them may be used in any combination.

The organoaluminum compound used in the treatment of the component (B-3) is not particularly limited. For example, an alkyl group-containing aluminum compound represented by the same formula as the general formula (IX) described below, A linear aluminoxane represented by the general formula (V) or a cyclic aluminoxane represented by the general formula (VI) or an aggregate of the cyclic aluminoxane can be preferably used. In terms of shellfish, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum,
Trialkylaluminum such as tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, dimethylaluminum hydroxide, diethylaluminum, etc., halogen, alkoxy or hydroxyl group-containing alkylaluminum Hydrogen-containing alkylaluminums such as dimethylaluminum hydride and diisobutylaluminum hydride, and aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. Of these, trimethylaluminum and triisobutylaluminum are particularly preferred.
The organoaluminum compound used in the treatment of the component (B-3) may be used alone or in combination of two or more.

The proportion of the silane compound and the organoaluminum compound used for the treatment of the component (B-3) is not particularly limited. ) For 1 mole of hydroxyl group in the component,
Normally 0.1 to 10000 silicon atoms in the silane compound
0 mol, preferably in a ratio of 0.5 to 10000 mol, and when using an organoaluminide, aluminum atoms in the organoaluminum compound are usually 0.1 to 0.1 mol.
It is used in a proportion of 100,000 mol, preferably 0.5 to 10,000 mol. When the component (B-3) is other than clay or clay mineral, 1 g of the component (B-3)
At a ratio of 0.001 to 100 g of silicon atoms in the silane-based compound, and when an organoaluminum compound is used, the aluminum atom in the organoaluminum compound is 0.001 g.
It is preferable to use 001 to 100 g at a ratio. If the ratio is outside the above range, the polymerization activity may decrease.
The treatment of the component (B-3) may be performed in an inert gas such as nitrogen or a hydrocarbon such as pentane, hexane, toluene, or xylene. Furthermore, this treatment can be carried out at a polymerization temperature, and it is preferable that the treatment be carried out at a temperature between -30 ° C and the boiling point of the solvent used, particularly between room temperature and the boiling point of the solvent used.

In the polymerization catalyst of the present invention, the component (B) includes the component (B-1), the component (B-2),
The component (B-3) may be used alone, or may be used in combination. The proportions of the (A) catalyst component and the (B) catalyst component in the prepolymerized catalyst are as follows:
When the compound (B-1) is used as the catalyst component (B), the molar ratio is preferably in the range of 1: 1 to 1:10 ⁶ , more preferably 1:10 to 1:10 ^4. If the ratio is out of the range, the catalyst cost per unit weight polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably from 10: 1 to 1:10.
0, more preferably in the range of 2: 1 to 1:10. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. Also, (B-
3) When clay or clay mineral is used as the compound,
The molar ratio of the hydroxyl group in the catalyst component (A) to the hydroxyl group in the catalyst component (B) is preferably 1: 0.1 to 1: 100,000, and more preferably 1: 0.5 to 1: 10000. Further, when an ion-exchange layered compound is used as the compound (B-3), the ratio of the catalyst component (A) to the catalyst component (B) is preferably 1: 1 to 1: 100,000 by weight. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical.

The polymerization catalyst comprises the components (A) and (B)
It may contain a component as a main component, or may contain an organoaluminum compound (C) together with the components (A) and (B). here,
As the organoaluminum compound of the component (C), a compound represented by the following general formula (IX): R ³³ _s AlQ _3-s (IX) (wherein, R ³³ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom, C1-C20 alkoxy group, C6-C20
Represents an aryl group or a halogen atom, and s is an integer of 1 to 3. However, a plurality of R ³³ may be the same or different. ) Or an aluminoxane.

Specific examples of the compound represented by formula (IX) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The use ratio of the (A) catalyst component and the (C) catalyst component is preferably 1: 1 to 1:20 in molar ratio.
00, more preferably 1: 5 to 1: 1000, and still more preferably 1:10 to 1: 500. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least the catalyst component
One can be used by supporting it on a suitable carrier. The charge
There is no particular limitation on the type of body, inorganic oxide carrier,
Use any other inorganic or organic carrier
Can be formed, but in particular, inorganic oxide carrier or other
Organic carriers are preferred. As the inorganic oxide carrier, specifically,
Is SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO
_Two, Fe_TwoO_Three, B_TwoO_Three, CaO, ZnO, BaO,
ThO_TwoAnd mixtures thereof, such as silica alumina and zeolite.
Olite, ferrite, sepiolite, glass fiber
-And the like. Among them, especially SiO 2_Two,
Al _TwoO_ThreeIs preferred. Incidentally, the inorganic oxide carrier,
It may contain a small amount of carbonate, nitrate, sulfate and the like.

On the other hand, as a carrier other than the above, MgC
_{l 2, Mg (OC 2 H} 5) such as magnesium compounds and their complex salts represented by the general formula MgR ³⁴ _{X X} ⁸ _y represented by magnesium compounds such as ₂ can be cited.
Here, R ³⁴ is an alkyl group having 1 to 20 carbon atoms and 1 carbon atom.
And X ⁸ is a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y =
2. Each R ³⁴ and each X ⁸ may be the same,
They may also be different. Also, as an organic carrier,
Examples include polymers such as polystyrene, substituted polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, and polyarylate, starch, and carbon. As the carrier used here,
MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ )
₂ , SiO ₂ and Al ₂ O ₃ are preferred. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 µm, preferably 10 to 200 µm, more preferably 20 to 100 µm. If the particle size is small, the fine powder in the polymer increases, and if the particle size is large, the coarse particles in the polymer increase, causing a decrease in bulk density and clogging of a hopper. The specific surface area of the carrier is usually 1 to 1000 m.
² / g, preferably 50 to 500 m ² / g, a pore volume of usually 0.1 to 5 cm ³ / g, preferably 0.3~3cm ³ /
g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. In addition,
The specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (see Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). ).

Further, the above-mentioned carrier is usually 120 to 100.
It is desirable to use by firing at 0 ° C, preferably 140 to 800 ° C. When at least one of the catalyst components is supported on the carrier, it is desirable to support at least one of the catalyst components (A) and (B), preferably both the catalyst components (A) and (B). . The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with the carrier, Is treated with an organoaluminum compound or a halogen-containing silicon compound, and then mixed with at least one of the component (A) and the component (B) in an inert solvent, by mixing the carrier with the component (A) and / or the component (B). A method of reacting an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A) with the component (A). A method in which the contact reaction product with the component (B) is mixed with the carrier, a method in which the carrier coexists in the contact reaction between the component (A) and the component (B), and the like can be used. Note that, in the above and the above reactions,
An organoaluminum compound as the component (C) can be added. The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is.

In the present invention, the component (A)
The operation of loading the component (B) on at least one carrier is polymerized.
By performing the reaction in the system, a catalyst can be generated.
For example, it shares with at least one of the component (A) and the component (B).
Body and, if necessary, organic aluminum of component (C)
And a raw material monomer at normal pressure to 20 kg / cm ^Two
In addition, reserve weight at -20 to 200 ° C for about 1 minute to 10 hours.
Can be used to produce catalyst particles.
You. In the present invention, the compound (B-1) is
The use ratio with the body is preferably 1: 0.5 to 1: 1000.
0, more preferably 1: 1 to 1: 500
The proportion of the component (B-2) and the carrier used is in weight ratio.
Preferably 10^-7: 1-10^-2: 1, more preferably 1
0^-Five: 1-10^-3: 1 is desirable. Also, (B
-3) The use ratio of the component and the carrier is preferably in a weight ratio.
1:10 to 1: 10000, more preferably 1:10
It is desirable to set 1: 1,000. In addition, the component (A)
The use ratio with the carrier is preferably 1: 5 to 1: by weight ratio.
1,000,000, more preferably 1:10 to 1: 100
00 is desirable.

The component (B) [component (B-1), (B-
2) Component or (B-3) component] and a carrier, and
Means that the ratio of the component (A) to the carrier is outside the above range.
In some cases, the activity may decrease. Prepared in this way
The average particle size of the polymerization catalyst obtained is usually from 2 to 200 μm,
Preferably 10 to 150 μm, particularly preferably 20 to 10 μm
0 μm, and the specific surface area is usually 20 to 1000 m^Two/
g, preferably 50 to 500 m^Two/ G. Average particle size
Is less than 2 μm, the fine powder in the polymer may increase.
Yes, over 200 μm, coarse particles in polymer increase
May be. Specific surface area is 20m^Two/ G
Activity may decrease, 1000m ^Two/ G
And the bulk density of the polymer may decrease. The catalyst
, The amount of transition metal in 100 g of the support is usually 0.05
It is preferably from 10 to 10 g, particularly preferably from 0.1 to 2 g. transition
If the amount of metal is outside the above range, the activity may decrease.
You. By supporting on a carrier in this way, industrially useful
To obtain a polymer with an advantageous high bulk density and excellent particle size distribution
be able to.

In the case of producing the propylene-based graft copolymer (II), it is desirable to use a polymerization catalyst that does not form a double bond at the terminal from the above-mentioned polymerization catalysts. As the polymerization catalyst, in addition to the polymerization catalyst described above, a solid catalyst component comprising titanium, magnesium and an electron donating compound, a polymerization catalyst comprising an organoaluminum compound and an electron donating compound as a third component (hereinafter simply referred to as “catalyst”). Titanium-magnesium catalyst). Here, the solid catalyst component comprises at least (a) a titanium compound, (b) a magnesium compound, and (c) an electron donating compound. As the titanium compound used as the component (a), for example, the general formula TiX ⁹ _t (OR ³⁵ ) _4-t (wherein
X ⁹ is a halogen atom, R ³⁵ is a hydrocarbon group having 1 to 10 carbon atoms, and t is an integer of 0 to 4. When a plurality of OR ³⁵ are present, each R ³⁵ may be the same or different. )). Examples of such a titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium Such as tetraalkoxytitanium, titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium Trihalogenated monoalkoxytitanium such as tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxy Monohalogenated trialkoxy titanium such as titanium dichloride, diethoxy titanium dibromide, etc .; However, among these, a titanium compound having a high halogen content, particularly titanium tetrachloride is preferred. Further, these titanium compounds may be used alone or in combination of two or more.

The magnesium compound of the component (b) in the solid catalyst component may be, for example, a compound of the general formula Mg
R ³⁶ R ^{37 wherein} R ³⁶ and R ³⁷ each represent a halogen atom, a hydrocarbon group or an OR group (R is a hydrocarbon group), and they may be the same or different. ] Can be mentioned. In the above general formula, examples of the halogen atom in R ³⁶ and R ³⁷ include chlorine, bromine, iodine and fluorine atoms. Examples of the hydrocarbon group of R ³⁶ and R ³⁷ and the hydrocarbon group represented by R include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a
And aralkyl groups having 7 to 12 carbon atoms.

Examples of such magnesium compounds include dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, butyl ethyl magnesium, diphenyl magnesium, dicyclohexyl magnesium, dimethoxy magnesium,
Diethoxymagnesium, dibutoxymagnesium, dihexoxymagnesium, dioctoxymagnesium,
Diphenoxy magnesium, dicyclohexoxy magnesium, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium bromide Butylmagnesium iodide, ethoxymagnesium chloride, butoxymagnesium chloride,
Hexoxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide and the like.

The magnesium compound can also be prepared from metallic magnesium or other magnesium compounds. Examples of such a method include the use of a halide and a general formula X _n M (OR ³⁸ ) _{mn in} metallic magnesium.
(In the formula, X is a hydrogen atom, a halogen atom or a carbon atom having 1 to
20 hydrocarbon groups, M is boron, carbon, aluminum,
A silicon or phosphorus atom, R ³⁸ represents a hydrocarbon group having 1 to 20 carbon atoms, m represents a valence of M, and n represents an integer of 0 or more and less than m.
And a plurality of X, each X may be the same or different, and if the OR ³⁸ there are a plurality, each OR ³⁸ may be the same or different. A) contacting the compound containing an alkoxy group represented by the formula (1) with a halide. In this general formula, examples of the carbon group having 1 to 20 carbon atoms and the carbon group having 1 to 20 carbon atoms represented by R ³⁸ include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl, isobutyl, hexyl, octyl and other alkyl groups having 1 to 20 carbon atoms, cyclohexyl groups and other cycloalkyl groups having 5 to 20 carbon atoms, allyl groups, propenyl groups and butenyl groups. An aryl group having 6 to 20 carbon atoms such as an alkenyl group having 2 to 20 carbon atoms, a phenyl group, a tolyl group and a xylyl group; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group and a 3-phenylpropyl group; No. Among these, an alkyl group having 1 to 10 carbon atoms is particularly preferable.

As another example, the general formula Mg (O
R ³⁹ ) ₂ (where R ³⁹ represents a hydrocarbon group having 1 to 20 carbon atoms and two OR ³⁹ may be the same or different), and a halide is brought into contact with a magnesium alkoxy compound represented by the formula: Method. In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by R ^39, a methyl group, an ethyl group, n- propyl group,
An alkyl group having 1 to 20 carbon atoms such as an isopropyl group, an n-butyl group, an isobutyl group, a hexyl group, and an octyl group;
C6-C20 aryl such as cycloalkyl group having 5-20 carbon atoms such as cyclohexyl group, alkenyl group having 2-20 carbon atoms such as allyl group, propenyl group and butenyl group; phenyl group, tolyl group and xylyl group; And aralkyl groups having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a 3-phenylpropyl group. Among these, an alkyl group having 1 to 10 carbon atoms is particularly preferable. Examples of the halide in these methods include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, hydrogen chloride and the like. Among them, silicon tetrachloride is particularly preferred. The magnesium compound (b) may be used alone or in combination of two or more.
It may be used by being supported on a support such as silica, alumina or polystyrene, or may be used as a mixture with a halogen compound or the like.

Further, (c) in the above solid catalyst component
Examples of the electron donating compound include alcohols, phenols, ketones, aldehydes, organic acids, and esters of organic and inorganic acids, and ethers such as monoether, diether, and polyether. Examples include oxygen electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. Of these, ester compounds of polycarboxylic acids, particularly diester derivatives of aromatic dicarboxylic acids, are preferred. . Here, the diester derivative of the aromatic dicarboxylic acid is preferably one in which the organic group in the ester portion is a linear, branched, or cyclic aliphatic hydrocarbon group.

Examples of such a compound include phthalic acid; naphthalene-1,2-dicarboxylic acid;
2,3-dicarboxylic acid; 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid; 5,6,7,8-
Tetrahydronaphthalene-2,3-dicarboxylic acid; indane-4,5-dicarboxylic acid; methyl such as indane-5,6-dicarboxylic acid; ethyl; n-propyl; isopropyl; n-butyl; isobutyl, t-butyl; 1-methylbutyl; 2-methylbutyl; 3-methylbutyl; 1,1-dimethylpropyl; 1-methylpentyl; 2-methylpentyl; 3-methylpentyl;
2-methylbutyl; n-hexyl; cyclohexyl; n-heptyl; n-octyl; n-nonyl; 2-methylhexyl; 3-methylhexyl; 4-methylhexyl; Diethyl esters such as -ethylhexyl; 3-ethylhexyl; 4-ethylhexyl; 2-methylpentyl; 3-methylpentyl; 2-ethylpentyl; and 3-ethylpentyl. Among these, phthalic acid diester derivatives are particularly preferred, and those in which the organic group in the ester portion is a linear or branched alkyl group having 4 or more carbon atoms are preferred. Specific examples thereof include di-n-butyl phthalate and diethyl phthalate.

The electron donating compound of the component (c) may be used alone or in combination of two or more.
The solid catalyst component in the titanium-magnesium catalyst used in the present invention is prepared by contacting the titanium compound (a), the magnesium compound (b) and the electron-donating compound (c). be able to. In this case, the molar ratio of the electron donating compound to the magnesium atom is usually 0.01 to 10, preferably 0.1 to 10.
It is advantageous to make contact so as to be 0.5 to 1.0, and it is preferable that the titanium compound is contacted so that the molar ratio to magnesium atom is usually 0.5 to 100, preferably 1 to 50. It is advantageous. The contact temperature is not particularly limited, but is usually −20 to 200 ° C., preferably 20 to 150 ° C.
It is selected in the range of ° C. The contact time depends on the contact temperature and the like, and cannot be determined unconditionally. However, it is usually about 1 minute to 24 hours, preferably about 10 minutes to 6 hours. The contact procedure is not particularly limited, and can be performed by various procedures.

After contacting each component, the solid catalyst component may be washed with an inert solvent such as a hydrocarbon. Further, at the time of the contact, it may be diluted with an inert solvent such as a hydrocarbon.
Further, it is preferable that the contact and the reaction of the titanium compound are performed twice or more, and the titanium compound is sufficiently supported on the magnesium compound serving as a catalyst carrier. The solid catalyst component thus prepared may be stored in a dry state or may be stored in an inert solvent such as a hydrocarbon. Further, the solid catalyst component, (a) component, in addition to component (b) and (c) component, as optionally component (d), for example, the general formula R ⁴⁰
_a R ⁴¹ _b Si (OR ⁴² ) _{4- ab} (where R ⁴⁰ , R ⁴¹ and R ⁴² each represent a hydrocarbon group having 1 to 20 carbon atoms;
They can be the same or different, a and b each represent 1 or 2, and their sum is 3 or less. )
Can also be used. Here, as the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴⁰ , R ⁴¹ and R ⁴² in the above general formula, for example, straight-chain groups such as methyl group, ethyl group, n-propyl group, n-butyl group and the like can be used. Chain hydrocarbon group, isopropyl group, isobutyl group, tert-
Branched hydrocarbon groups such as butyl group and sec-butyl group,
Alternatively, a cyclic hydrocarbon group, a vinyl group, an aryl group and the like can be mentioned. Examples of the cyclic hydrocarbon group include a cyclopentyl group; a 2-methylcyclopentyl group; a 3-methylcyclopentyl group; a 2-ethylcyclopentyl group;
n-propylcyclopentyl group; 2,3-dimethylcyclopentyl group; 2,4-dimethylcyclopentyl group;
2,5-dimethylcyclopentyl group; 2,3-diethylcyclopentyl group; 2,4-diethylcyclopentyl group; 2,5-diethylcyclopentyl group; 2,3,4-
2,3,5-trimethylcyclopentyl group; 2,3,4-triethylcyclopentyl group; tetramethylcyclopentyl group; tetraethylcyclopentyl group; cyclohexyl group; 2-methylcyclohexyl group; 3-methylcyclohexyl group; Methylcyclohexyl group; 2-ethylcyclohexyl group; 2
-N-propylcyclohexyl group; 2,3-dimethylcyclohexyl group; 2,4-dimethylcyclohexyl group;
2,5-dimethylcyclohexyl group; 2,6-dimethylcyclohexyl group; 2,3-diethylcyclohexyl group; 2,4-diethylcyclohexyl group; 2,5-diethylcyclohexyl group; 2,6-diethylcyclohexyl group; 3,4-trimethylcyclohexyl group; 2,
2,5-trimethylcyclohexyl group; 2,3,6-trimethylcyclohexyl group; 2,4,5-trimethylcyclohexyl group; 2,4,6-trimethylcyclohexyl group; 2,3,4-triethylcyclohexyl group;
3,4,5-tetramethylcyclohexyl group; 2,3
4,6-tetramethylcyclohexyl group; 2,3,5
6-tetramethylcyclohexyl group; 2,3,4,5-
A tetraethylcyclohexyl group; a pentamethylcyclohexyl group; a pentaethylcyclohexyl group.

Further, R⁴⁰, R⁴¹And OR⁴²But each
If there is more than one, each R⁴⁰May be the same or different,
Also each R⁴¹May be the same or different. In addition, each
OR ⁴²May be the same or different. Such organic
Examples of the silicon compound include di-t-butyldimethoxysila
, T-butylethyldimethoxysilane, dicyclopen
Tyldimethoxysilane, dicyclohexyldimethoxysi
Orchid, di (2-methylcyclopentyl) dimethoxysila
, Di (3-methylcyclopentyl) dimethoxysila
Di, 2- (2-ethylcyclopentyl) dimethoxysila
, Di (3-ethylcyclopentyl) dimethoxysila
Di (2,3-dimethylcyclopentyl) dimethoxy
Silane, methyltrimethoxysilane, ethyltrimethoxy
Sisilane, methyltriethoxysilane, ethyltriet
Xysilane, propyltriethoxysilane, isopropyl
Rutriethoxysilane, butyltriethoxysilane, i
Sobutyl triethoxysilane, t-butyl triethoxy
Silane, hexyltriethoxysilane, propyltrip
Ropoxysilane, isopropyltrimethoxysilane,
Tyrulutrimethoxysilane, isobutyltrimethoxysi
Orchid, t-butyltrimethoxysilane, hexyltrime
Toxisilane, dimethyldimethoxysilane, diethyldi
Methoxysilane, dipropyldimethoxysilane, diiso
Propyldimethoxysilane, dibutyldimethoxysila
, Diisobutyldimethoxysilane, di-t-butyldi
Methoxysilane, methylethyldimethoxysilane, methyl
Ru-t-butyldimethoxysilane, trimethylmethoxy
Silane, triethylmethoxysilane, tripropylmeth
Xysilane, triisopropylmethoxysilane, trib
Tyl methoxy silane, triisobutyl methoxy silane
Which alkylalkoxysilane, cyclopentyl trime
Toxysilane, cyclopentyltriethoxysilane, di
Cyclopentyldimethoxysilane, cyclohexyltri
Methoxysilane, dicyclohexyldimethoxysilane
Which cycloalkylalkoxysilane, phenyl trime
Toxysilane, phenyltriethoxysilane, diphenyl
Phenylalkoxysilane such as rudimethoxysilane
Can be mentioned. In addition, methylcyclopentyldimethyl
Toxysilane, methylcyclohexyldimethoxysila
T-butylcyclopentyldimethoxysilane, t-
Butylcyclopentyldimethoxysilane, t-butylsiloxane
Clohexyldimethoxysilane, cyclopentylcyclo
Hexyl dimethoxy silane can also be mentioned.
You. Among these, dicyclopentyldimethoxysila
, T-butylcyclopentyldimethoxysilane, di-
T-butyldimethoxysilane and the like are preferred. this
The organosilicon compound of component (d) may be used alone,
You may use it combining the above.

The above-mentioned titanium-magnesium catalyst comprises the above-mentioned solid catalyst component, an organoaluminum compound and an electron-donating compound as a third component. The organoaluminum compound as the component (C), for example, the organoaluminum compound represented by the general formula (IX) can be exemplified. Further, examples of the electron-donating compound as the third component include the same compounds as the electron-donating compound of the component (c) in the solid catalyst component described above.

The propylene copolymer (I) of the present invention comprises
It is also a precursor of the propylene-based graft copolymer (II) and is obtained by the reaction step [1], that is, the step of polymerizing propylene and diolefin in the presence of the polymerization catalyst. At this time, as a polymerization catalyst, a propylene-based copolymer (I) in which the product relationship between the total of vinyl groups and carbon-carbon double bonds observed in the copolymer and the intrinsic viscosity and the like are specified is obtained. The polymerization catalyst is appropriately selected from the above-mentioned polymerization catalysts. In this reaction step [1], the introduction of a carbon-carbon unsaturated group and the crosslinking reaction are caused by using a diolefin, and further, the diolefin has a carbon-carbon double bond residue derived from a diolefin, In addition, the reaction for generating an unsaturated group such as a terminal vinyl group derived from an active olefin terminal proceeds. The charging ratio of propylene with diolefins, diolefins / Puropyinmoru ratio, usually 1/10 ^{6-10 2/1,} preferably 1 /
Both components are used so as to be in the range of 10 ⁴ to 10/1. The ratio of the monomer component and the catalyst component in the reaction step [1], the monomer component / (A) catalyst component molar ratio is usually 10 ⁷ / 1-10 / 1, preferably 10 ⁵ / 1-1
0 chosen ^2/1 to become so. The polymerization pressure is usually selected from the range of normal pressure to 30 kg / cm ² · G, and the polymerization temperature is preferably higher as long as the catalyst activity is not impaired.
Usually -100 to 300C, preferably -50 to 200
° C, more preferably in the range of 10 to 180 ° C.

The propylene-based copolymer (I) of the present invention thus obtained is a long-chain branched copolymer composed of units derived from propylene and units derived from diolefin, Average molecular weight of 1500 to 50,000
0, preferably 2000 to 400,000, more preferably 3000 to 350,000. The propylene-based copolymer (I) of the present invention can be converted into a sufficiently high-molecular-weight graft copolymer by graft polymerization of a monomer such as propylene, even when the weight average molecular weight is relatively low. it can. The weight average molecular weight is a molecular weight in terms of polyethylene measured by gel permeation chromatography (GPC). The unit content derived from diolefin in the copolymer (I) is 0.
More than 20 mol%, preferably 0.1 to 18 mol%
Mol%, more preferably in the range of 0.2 to 16 mol%. When the content is 0 mol%, the crosslinking reaction and the amount of pendant unsaturated residues are small, and the grafting efficiency in the reaction step [2] described below is low. On the other hand, if it exceeds 20 mol%, the crosslinking reaction tends to occur excessively and tends to become infusible.

In the propylene copolymer (I), the sum [C] (mol%) of the vinyl group derived from propylene and the carbon-carbon double bond derived from diolefin is 13%.
It is necessary that the product of intrinsic viscosity [η] (deciliter / g) measured in decalin at 5 ° C. satisfies 0.01 ≦ [η] · [C] ≦ 5. This [η] · [C] is 0.
If it is less than 01, the number of substantial reaction points in the subsequent graft reaction is small, and the carbon-
It is highly possible that the carbon double bond has also been lost by the crosslinking reaction. Therefore, even if the next grafting reaction is performed, it does not show sufficient activation energy for melt flow and cannot be used as a compatibilizer. On the other hand, [η]
When [C] exceeds 5, a large number of substantial reaction points in the graft reaction are present, so that a gel or the like is generated,
Not preferred. From such a viewpoint, preferably 0.015 ≦ [η] · [C] ≦ 4.5, more preferably 0.018 ≦ [η] · [C] ≦ 4, particularly preferably 0.02 ≦ [η] · [C] ≦ 3.5.

Here, the propylene-based copolymer (I)
The terminal vinyl group derived from propylene and the carbon-carbon double bond derived from diolefin present in can be calculated as follows. (1) When the diolefin is a linear or branched acyclic diene compound: Calculated based on the measurement result of the infrared absorption spectrum by the following method. That is, a propylene-based copolymer (I) was formed into a film having a thickness of about 100 μm by hot pressing, and the transmittance of a peak at 907 cm ⁻¹ was measured with an infrared spectrophotometer. Analytical Handbook, edited by the Japan Society for Analytical Chemistry, p. 240]. [C] = 1.14 × log (I ₀ / I) × (1 / (D ×
T)) In the formula, each symbol indicates the following. [C]; number of terminal vinyl groups and carbon-carbon double bonds derived from diolefins (pieces / 1000 carbons) I ₀ ; transmittance at baseline I; transmittance at 907 cm ⁻¹ D; density of polymer (g / Cm ³ ) T; Film thickness (mm) (2) When diolefin other than the above (1) is used: The terminal vinyl group and the α-olefinic carbon-carbon double bond derived from diolefin are It can be calculated as in (1) above. Other carbon-carbon double bonds can be formed per 1000 carbon atoms in the main chain by a conventional method by measurement of nuclear magnetic resonance spectrum, that is, 50 monomer repeating units.
It is calculated as the number per zero. The sum of the measured values calculated in this way is defined as [C]. The intrinsic viscosity [η] was measured in a decalin solvent at a temperature of 135 ° C., and calculated using the Haggins equation. The Haggins constant was 0.35.

The propylene-based copolymer (1) of the present invention may have no melting point or a specific melting point range as measured by a differential scanning calorimeter (DSC). The propylene copolymer (1) that does not show a melting point is
It has an atactic structure that does not show the stereoregularity of the propylene chain. In addition, the propylene-based copolymer (1) having a specific melting point range has an isotactic structure in which the stereoregularity of the propylene chain is an isotactic structure. The selection of the atactic structure or the isotactic structure can be performed as required from the viewpoint of heat resistance and flexibility. When heat resistance is required, an isotactic structure is advantageous, and the melting point measured by a differential scanning calorimeter (DSC) is 50 to 16.
It is preferably in the range of 5 ° C. If it is lower than 50 ° C., sufficient heat resistance is not exhibited, and it is still technically difficult to exceed 165 ° C. This melting point is measured as follows.
That is, a differential scanning calorimeter (manufactured by PerkinElmer)
Using DSC7), 10 mg of a sample was previously melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then 0 ° C. at 10 ° C./min.
Cool down to After further holding at this temperature for 3 minutes, 10
The peak top of the maximum peak of the melting endothermic curve obtained by increasing the temperature at a rate of ° C./min was defined as the melting point. The propylene-based copolymer (I) of the present invention has 2 to 2 carbon atoms excluding propylene.
The content of units derived from 20 α-olefins, cyclic olefins and styrene monomers is 50 mol% or less, preferably 0 to 40 mol% of the whole. Here, if it exceeds 50 mol%, the vinyl group content in the copolymer decreases,
There is a problem that the graft efficiency is reduced.

On the other hand, the propylene-based graft copolymer (II) of the present invention is used in the reaction step [2], that is, the propylene-based copolymer (I) obtained in the reaction step [1] is added to the propylene-based graft copolymer (I). In the presence, it can be obtained by a step of copolymerizing (grafting) at least one of an α-olefin having 2 to 20 carbon atoms, a cyclic olefin, and a styrene monomer. The propylene-based copolymer (I) was not separated,
When the reaction steps [1] and [2] are performed continuously, it is not necessary to newly add a polymerization catalyst. Here, the monomer to be copolymerized (grafted) with the propylene-based copolymer (I) is, as described above, at least one of an α-olefin having 2 to 20 carbon atoms, a cyclic olefin, and a styrene-based monomer. Of these, propylene is the most preferred. For specific examples of the α-olefin having 2 to 20 carbon atoms, cyclic olefin and styrene-based monomer,
This is the same as that already mentioned in the description of the propylene-based copolymer (I).

The content of the propylene polymer (I) segment in the propylene graft copolymer (II) of the present invention is 0.01 to 80% by weight, preferably 0.1 to 80% by weight.
It is preferably in the range of 1 to 70% by weight, more preferably 0.5 to 65% by weight. If the content is more than 80% by weight, the graft portion is small and the desired processing characteristics cannot be obtained. If the content is less than 0.01% by weight, the desired processing characteristics cannot be obtained. The propylene-based graft copolymer (II) has a boiling xylene-insoluble portion of 1% or less, preferably 0.8% or less, and contains substantially no gel. Here, the boiling xylene-insoluble portion is expressed as a percentage of the weight of the residue left on the filter paper by extracting the finely divided propylene-based graft copolymer with xylene for 8 hours by the Soxhlet extraction method. Further, the copolymer chain produced in the reaction step [2] has a high degree of randomness as a result of ¹³ C-NMR structural analysis. The relationship between the melting point and the comonomer content is different from that of the conventional propylene-based copolymer.

In the present invention, the propylene-based copolymer (I) and the propylene-based graft copolymer (II)
Can be subjected to a hydrogenation treatment in order to make it more excellent in thermal stability. In the present invention, a preferred propylene-based graft copolymer (II) is a propylene-based graft copolymer having a content of units derived from propylene of 60 to 99.99 mol% and a density of 0.2. 80
To 0.95 g / cm ³ and a crystallization enthalpy of 20 J / g or more. The density can be controlled over a wide range by the content of units derived from α-olefins such as 1-butene and 1-octene, and the density and content of the propylene copolymer (I). . The crystallization enthalpy decreases with an increase in the comonomer unit content, and can be controlled by the presence or absence of crystallinity of the propylene-based copolymer (I), its degree, and the content of the copolymer (I). The enthalpy of crystallization is obtained by melting the sheet pressed at 190 ° C. for 5 minutes at 150 ° C. and then lowering the temperature to −50 ° C. at a rate of 10 ° C./min. It is a value measured by a meter and calculated from the area of the crystallization peak.

The propylene-based graft copolymer (II) of the present invention has an activation energy (Ea) of melt flow in the range of 8 to 25 kcal / mol, and has an activation energy in air obtained by thermogravimetric analysis. 5% weight loss temperature 300
C. or higher, preferably 310.degree. C. or higher is desirable. The activation energy (Ea) of the melt flow can be arbitrarily controlled to impart processing characteristics from injection molding to blow molding and film molding, so Ea is a very important index. The activation energy (Ea) can be calculated as follows. That is, measurement temperatures of 150 ° C., 170 ° C., 190 ° C.
The frequency dependence of the dynamic viscoelasticity at 10 ° C., 210 ° C. and 230 ° C. (10 ⁻² to 10 ² rad / sec) was measured.
Using 0 ° C. as a reference temperature, the activation energy (Ea) is calculated by the Arrhenius equation from the shift factor of G ′, G ″ at each temperature and the reciprocal of the absolute temperature using the temperature-time conversion rule.

As for thermal stability, generally, carbon-
The polymer having a carbon-unsaturated group has low thermal stability, is inferior in molding processability, further deteriorates in weather resistance, and requires a complicated additive formulation. However, the propylene-based graft copolymer (II )), A material having a 5% weight loss temperature of 300 ° C. or higher, preferably 305 ° C. or higher can be obtained, and the above problem can be solved. The 5% weight loss temperature is the temperature at the time of 5% weight loss when the temperature is increased at a rate of 10 ° C./min in an air flow rate of 300 ml / min. The propylene-based copolymer (I) has a sufficiently improved melt flow activation energy (Ea) as compared with a propylene homopolymer having substantially the same weight average molecular weight, and is excellent in processing characteristics. .

The propylene-based copolymer (I) and the propylene-based graft copolymer (II) of the present invention can be used by being mixed with another thermoplastic resin. Other thermoplastic resins include, for example, polyolefin-based resins, polystyrene-based resins, condensation-based polymers, and addition-polymerized polymers. Specific examples of the polyolefin resin include high-density polyethylene, low-density polyethylene, poly-3-methyl-1-butene, and poly-4-methyl-1-.
Pentene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-
Linear low-density polyethylene obtained using methyl-1-butene, etc., ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Polymer,
Ethylene ionomers, polypropylene and the like can be mentioned. Specific examples of the polystyrene resin include general-purpose polystyrene, isotactic polystyrene, and high-impact polystyrene (modified with rubber). Specific examples of the condensation polymer include polyacetal resin, polycarbonate resin, nylon 6, nylon 6,
And the like, polyamide resins such as No. 6, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resins, polyimide resins, polysulfone resins, polyetherphone resins, and polyphenylene sulfide resins. Examples of the addition polymerization type polymer include a polymer obtained from a polar vinyl monomer and a polymer obtained from a diene monomer, specifically, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, and acrylonitrile. -Butadiene-styrene copolymers, diene-based polymers in which diene chains are hydrogenated, and thermoplastic elastomers. Among these thermoplastic resins, polyolefin resins are preferred.

[0090]

Next, the present invention will be described in more detail with reference to examples.
As will be explained, the present invention is in no way limited by these examples.
It is not something to be done. Example 1 A propylene / 1,9-decadiene copolymer (propylene
Of 1.4-liter stainless steel pressure-resistant autoclave with stirrer
After drying and replacing the nitrogen with nitrogen, dry toluene 4
00 ml, 1,9-decadiene 15 mmol,
0.5 mmol of triisobutylaluminum, methyl alcohol
Add 5 mmol of minoxane and stir at 500 rpm
Starting, the temperature of the reaction system was brought to 60 ° C. Next, (1,
2'-ethylene) (2,1'-ethylene) -bis (in
Denenyl) hafnium dichloride [Et_Two(Ind)_TwoH
fCl_Two] In a toluene solution of 10
Micromolar was added. 3 kg / c propylene
m ^TwoG continuously feed and carry out copolymerization for 240 minutes
Was. After the reaction is completed, unreacted propylene is removed by depressurization
And pour the reaction mixture into a large amount of methyl alcohol
Deactivate the catalyst and separate and dry to produce propylene / 1,9-
37.4 g of decadiene copolymer was obtained. About this copolymer
And evaluated,¹³Determined from C-NMR
The 1,9-decadiene content was 2.2 mol%,
The stereoregularity of the Len chain was 78 in mm. Also the pole
Terminal vinyl content obtained from limiting viscosity and infrared absorption spectrum
The product [η] · [C] was 0.224. Table 1 shows the results
Shown in

Example 2 Production of propylene / 1,9-decadiene copolymer (propylene-based copolymer (I)) Except that the amount of 1,9-decadiene copolymer added in Example 1 was changed to 7 mmol. Was carried out in the same manner as in Example 1. About the obtained copolymer, the same measurement as Example 1 was performed. The results are shown in Table 1.

Example 3 Production of a Graft Copolymer of Propylene with the Copolymer Obtained in Example 1 (Propylene Graft Copolymer (II)) A stainless steel pressure-resistant autoclave equipped with a stirrer was dried and replaced with nitrogen. After that, 400 ml of dehydrated toluene, 50 ml of a dehydrated toluene solution of 3 g of the copolymer obtained in Example 1, and 0.1 ml of triisobutylaluminum were added.
5 mmol and 0.8 mmol of methylaluminoxane were added, stirring was started at 500 rpm, and the temperature of the reaction system was reduced to 40.
° C. Next, rac-dimethylsilanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride [rac-SiMe ₂ (2-Me
[-4,5-BenzoInd) ₂ ZrCl ₂ ] was added in an amount of 0.5 μmol in terms of zirconium atom, and propylene was continuously supplied at 7 kg / cm ² G to carry out polymerization for 60 minutes. After completion of the reaction, unreacted propylene was removed by depressurization, the catalyst was deactivated by pouring the reaction mixture into a large amount of methyl alcohol, and separated and dried to obtain 120 g of a propylene-based graft copolymer. When this graft copolymer was evaluated, ¹³
The stereoregularity of the propylene chain determined from C-NMR is m
It was 92.5 in mmm. Further, the melting point was 146 ° C., there was no boiling xylene-insoluble portion, and the activation energy of the melt flow was 12.5 kcal / mol.

Example 4 (1) Preparation of Toluene Suspension of Montmorillonite Treated with Silane Compound 40 g of commercially available montmorillonite (Kunimine F, manufactured by Kunimine Kogyo Co., Ltd.) was pulverized by a pulverizer for 4 hours. 20 g of crushed montmorillonite was placed in a 500 ml three-necked flask, and 100 ml of ion-exchanged water in which 20 g of magnesium chloride hexahydrate was dissolved was added and dispersed. The mixture was treated at 90 ° C. for 0.5 hour with stirring. After treatment,
The solid component obtained by filtration was washed three times with 100 ml of water. This magnesium chloride treatment and water washing were repeated once. Next, this solid component is added with 6% hydrochloric acid 16
The mixture was dispersed in 0 ml and treated under reflux with stirring for 2 hours. After the treatment, the solid component obtained by filtration was repeatedly washed with water until the filtrate became neutral, and dried under vacuum at room temperature to obtain chemically treated montmorillonite. 1.0 g of this chemically treated montmorillonite was placed in a 300 ml Schlenk tube, and 25 ml of toluene was added to disperse it. To this, 1.13 g (5.2 mmol) of methylphenethylsilyl dichloride was added, and the mixture was stirred at room temperature for 60 hours and then at 100 ° C. for 1 hour.
After completion of the stirring, the operation was allowed to stand, the supernatant liquid was extracted, 200 ml of toluene was added to the remaining solid component, and the mixture was stirred. The operation of allowing the mixture to stand and extract the supernatant liquid was repeated three times. Toluene was added to the obtained solid to make the total amount 50 ml, and a suspension was prepared. (2) Production of propylene / 1,9-decadiene copolymer (propylene-based copolymer (I)) In Example 1, montmorillonite treated with the silane compound obtained in (1) above in place of 5 mmol of methylaluminoxane The same procedure as in Example 1 was carried out except that 5 ml of the suspension was added, the polymerization temperature was changed to 50 ° C., and the polymerization time was set to 300 minutes. About the obtained copolymer, Example 1
The same measurement was performed. The results are shown in Table 1.

[0094]

[Table 1]

[0095]

As described above, the propylene-based copolymer (I) and the propylene-based graft copolymer (II) of the present invention
Can control the activation energy of the flow of the melt arbitrarily, enable high-speed molding, reduce processing costs, and have transparency and uniformity. Further, thereby, a novel branched propylene-based copolymer or propylene-based elastomer can be obtained. Further, the propylene-based copolymer (I) and the propylene-based graft copolymer (II) of the present invention
Is suitable for high-temperature molding and generates less gel in blow molding and film molding, and is also useful as a compatibilizer for other thermoplastic resins.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J026 AA11 AA12 AA13 AA14 AA17 AA18 AA19 AA67 AA72 AC22 AC33 AC34 AC36 BA01 BA02 BA03 BA05 BB01 BB02 DA17 DA19 DB17 DB19 EA08 GA01 GA02 4J028 AA01A AA02BA01A02BA01B BB02B BC01B BC08B BC09B BC12B BC15B BC25B BC32B BC40B CA30C CB91B CB98B EB01 EB04 EB15 EB16 EB17 EB18 EB21 EC02 EC04 FA02 GA01 GA16 4J100 AA02Q AA03P AA04Q AA05Q AA07Q AA15Q AA16Q AA17Q AA19Q AB08Q AB09Q AB10Q AB13Q AB15R AB16R AE81R AE83R AR09R AR11Q AR11R AR21R AR22R AS01R AU21R BC21R BC22Q BC23Q BC23R BC27Q BC27R BC36R BC37R CA04 CA05 DA01 DA09 DA39 DA62 FA08

Claims (6)

[Claims] 1. A polymer containing at least a terminal vinyl group derived from propylene and a carbon-carbon double bond derived from diolefin, wherein the following (a) to (d) (a) weight average molecular weight is 1500 to 500000,
(B) the content of units derived from diolefin is 0 mol%
(C) the content of units derived from α-olefins having 2 to 20 carbon atoms other than propylene, a cyclic olefin and a styrene monomer is 0 to 50 mol% and (d) a decalin solvent Of the intrinsic viscosity [η] (deciliter / g) measured in the above and the sum [C] of the content of the terminal vinyl group derived from propylene and the carbon-carbon double bond derived from the diolefin [C] [C] Satisfies 0.01 to 5. 2. A melting point observed by a measurement using a differential scanning calorimeter does not exist or the melting point is 50 to 165.
The propylene-based copolymer according to claim 1, which is in the range of ° C. 3. The propylene copolymer according to claim 1, which is obtained by graft-polymerizing an α-olefin having 2 to 20 carbon atoms, a cyclic olefin or a styrene monomer, and having a boiling xylene-insoluble portion of 1% or less. And contains substantially no gel, and the content of the propylene-based copolymer is 0.01 to 80.
A propylene-based graft copolymer in an amount of 1% by weight. (A) at least one selected from transition metal compounds belonging to Group 4 of the periodic table having a cyclopentadienyl group, (B) (B-1) an aluminum oxy compound, 2) a polymerization catalyst containing an ionic compound capable of converting to a cation by reacting with the above transition metal compound and (B-3) at least one selected from clays, clay minerals and ion-exchangeable layered compounds; The propylene-based copolymer according to claim 1, wherein propylene and a diolefin are copolymerized, or propylene and a diolefin are copolymerized with at least one of a cyclic olefin and a styrene-based monomer in the presence. A method for producing a propylene-based copolymer, characterized in that: 5. (A) at least one selected from transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl group, (B) (B-1) an aluminum oxy compound, 2) a first composition comprising at least one selected from the group consisting of an ionic compound which can be converted into a cation by reacting with the transition metal compound and (B-3) a clay, a clay mineral or an ion-exchangeable layered compound; In the presence of a polymerization catalyst,
The propylene and diolefin are copolymerized, or propylene and a diolefin are copolymerized with at least one of an α-olefin having 2 to 20 carbon atoms other than propylene, a cyclic olefin, and a styrene monomer. After the formation of the propylene-based copolymer of the above, in the presence of the above-mentioned first polymerization catalyst, or a solid catalyst component containing titanium, magnesium and an electron-donating compound as essential components, an organoaluminum compound and an electron as a third component The propylene graft according to claim 2, wherein the copolymer is further graft-polymerized with an α-olefin having 2 to 20 carbon atoms, a cyclic olefin or a styrene monomer in the presence of a second polymerization catalyst comprising a donor compound. A method for producing a propylene-based graft copolymer, which comprises producing a copolymer. 6. The transition metal compound of the component (A) is (A-
1) General formula (I)[Wherein, R¹~ R⁶Are independently a hydrogen atom and a halo
Gen atom, hydrocarbon group having 1 to 20 carbon atoms or 1 to carbon atoms
20 represents a halogen-containing hydrocarbon group;^ThreeAnd R ^Four, R
^FourAnd R^FiveAnd R^FiveAnd R⁶At least one pair of
May be bonded to form a ring;¹And X^TwoIs it
Each independently represents a hydrogen atom, a halogen atom or a carbon number of 1 to 20;
Y represents a hydrocarbon group of¹Is the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR'-, -PR '
-, -P (O) R'-, -BR'- or -AlR'-
R ′ is a hydrogen atom, a halogen atom, and has 1 to 20 carbon atoms.
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Represents a group. M¹Is titanium, zirconium or hafnium
Is shown. A transition metal compound represented by the general formula (A-2):
Formula (II)[Wherein, R⁷~ R¹³, R^Fifteen, R¹⁶, X^ThreeAnd X^FourIs
Each independently a hydrogen atom, a halogen atom, a carbon number of 1 to 20
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing
A group or a phosphorus-containing group;⁷And R⁸Joined to each other
To form a ring. R¹⁴, R¹⁷Are independent of each other
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogen-containing hydrocarbon groups, silicon-containing groups, and oxygen-containing
Indicates a group containing, sulfur-containing, nitrogen-containing or phosphorus-containing group.
You. Y^TwoIs a divalent bridging group connecting the two ligands.
A hydrocarbon group having 1 to 20 carbon atoms;
Hydrogen-containing hydrocarbon group, silicon-containing group, germanium-containing
Group, tin-containing group, -O-, -CO-, -S-, -SO _Two
-, -Se-, -NR'-, -PR'-, -P (O)
R′—, —BR′— or —AlR′—, wherein R ′ is water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
It represents a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. M^Two
Represents titanium, zirconium or hafnium. ]
Transition metal compound represented by the following general formula (A-3):[Wherein, R¹⁸Are the same or different and each represent a hydrogen atom,
20 alkyl groups, cycloalkyl having 3 to 20 carbon atoms
Group, alkenyl group having 2 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, an alkylaryl group having 7 to 20 carbon atoms, or
Represents an arylalkyl group having 7 to 20 carbon atoms,
Two R¹⁸Forms a ring of 5 to 8 carbon atoms
Well, R¹⁸Contains silicon or germanium atoms
You may. Y ^ThreeIs> SiR¹⁹ _TwoOr> GeR¹⁹ _Two(R¹⁹
Are the same or different and each have an alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having a prime number of 3 to 20;
Lucenyl group, aryl group having 6 to 20 carbon atoms, 7 to 7 carbon atoms
20 alkylaryl groups or aryls having 7 to 20 carbon atoms
And may optionally contain a heteroatom,
Two R¹⁹May form a cyclic group of up to 8 atoms
No. Provided that at least four carbon atoms are two R¹⁹Included
I will. ) And M^ThreeIs titanium, zirconium or ha
Indicates funium. X^FiveAnd X⁶Are the same or different
Logen atom, -OH, -SH, -R²⁰, -OR²⁰, -S
R²⁰, -NR²⁰ _TwoOr -PR²⁰ _Two(R²⁰Is R¹⁸Same as
Is shown. ). And (A-4) a general formula (IV):[Where M^ThreeIs titanium, zirconium or hafnium
Show, E¹And E^TwoAre each substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, heterocyclo
Pentadienyl group, substituted heterocyclopentadienyl
Group, amide group, phosphide group, hydrocarbon group and silicon-containing
A ligand selected from the group¹And A^TwoThrough
To form a crosslinked structure, and they
May be one or different, X⁷Represents a σ-binding ligand
X⁷If there are multiple Xs ⁷Are the same but different
Other X⁷, E¹, E^TwoOr Y^FourAnd crosslink
It may be. Y^FourRepresents a Lewis base;^FourIs multiple
If there is more than one Y^FourMay be the same or different,
Other Y^Four, E¹, E^TwoOr X⁷May be cross-linked,
A¹And A^TwoIs a divalent bridging group connecting the two ligands
A hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Halogen-containing hydrocarbon groups, silicon-containing groups, and germanium
-Containing group, tin-containing group, -O-, -CO-, -S-, -S
O_Two-, -Se-, -NR'-, -PR'-, -P
(O) R′-, -BR'- or -AlR'-,
R 'is a hydrogen atom, a halogen atom, a carbon atom having 1 to 20 carbon atoms.
Represents a hydrogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms.
However, they may be identical or different. q
Is an integer of 1 to 5 [(M^ThreeValence-2), and r
Represents an integer of 0 to 3. Is a transition metal compound represented by
6. At least one member selected from the group consisting of:
Manufacturing method.